Organometallic donor-acceptor complexes with nonplanar donors

The zigzag linear chain complex [(C6Me6)2M2+][iso-C 4(CN)6 2-] (M = Fe, Ru)

Michael Ward, J. C. Calabrese

Research output: Contribution to journalArticle

Abstract

Donor-acceptor solids [(C6Me6)2Me2+] [iso-C4(CN)6 2-]·MeNO2 (M = Fe, 1a; M = Ru, 2a) and [(C6Me3Hg)2M2+][iso-C 4(CN)6 2-] (M = Fe, 1b; M = Ru, 2b) prepared from (arene)2M2+ and iso-C4(CN)6 2- are described. Single-crystal X-ray studies show that Ia crystallizes in the space group P21/c with a = 19.875 (6) Å, b = 10.512 (2) Å, c = 15.981 (4) Å, β = 96.65 (3)°, V = 3316 (3) Å3, ρ = 1.36 g cm-3, Z = 4, Ru = 0.061, and Rw = 0.080. The ruthenium analogue 2a also crystallizes in the space group P21/c with a = 19.973 (2) Å, b = 10.553 (2) Å, c = 16.144 (1) Å, β = 96.80 (7)°, V = 3378 (3) Å3, ρ = 1.36 g cm-3, Z = 4, Ru = 0.070, and Rw = 0.068. Both complexes exhibit "zigzag" linear chains of closely spaced alternating cations and anions. Donor-acceptor interactions arise from close intermolecular contacts between the C6Me6 ligands of the dications and nitrogen atoms of the nonplanar dianion with dianions "bridging" the dications via three of its cyano groups. The complexes exhibit strong charge-transfer bands and are best described as donor-acceptor (DA) complexes with nominally doubly charged (D2-A2+) ground states and (D-A+) excited states. The difference between the charge-transfer absorption energies of 1 and 2 is equivalent to the difference in the solution reduction potentials of the isostructural (arene)2M2+ cations. The structure of the 19e (C6Me6)2Fe+ monocation, reported here for the first time, is essentially identical with that of the 18e dication, suggesting that the charge-transfer transitions of these DA complexes can occur without the formation of energetically unfavorable molecular conformations.

Original languageEnglish (US)
Pages (from-to)593-602
Number of pages10
JournalOrganometallics
Volume8
Issue number3
StatePublished - 1989

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Organometallics
Charge transfer
charge transfer
Cations
cations
Ruthenium
energy absorption
Excited states
nitrogen atoms
Ground state
ruthenium
Anions
Conformations
Nitrogen
Single crystals
analogs
anions
Ligands
X rays
Atoms

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

Organometallic donor-acceptor complexes with nonplanar donors : The zigzag linear chain complex [(C6Me6)2M2+][iso-C 4(CN)6 2-] (M = Fe, Ru). / Ward, Michael; Calabrese, J. C.

In: Organometallics, Vol. 8, No. 3, 1989, p. 593-602.

Research output: Contribution to journalArticle

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title = "Organometallic donor-acceptor complexes with nonplanar donors: The zigzag linear chain complex [(C6Me6)2M2+][iso-C 4(CN)6 2-] (M = Fe, Ru)",
abstract = "Donor-acceptor solids [(C6Me6)2Me2+] [iso-C4(CN)6 2-]·MeNO2 (M = Fe, 1a; M = Ru, 2a) and [(C6Me3Hg)2M2+][iso-C 4(CN)6 2-] (M = Fe, 1b; M = Ru, 2b) prepared from (arene)2M2+ and iso-C4(CN)6 2- are described. Single-crystal X-ray studies show that Ia crystallizes in the space group P21/c with a = 19.875 (6) {\AA}, b = 10.512 (2) {\AA}, c = 15.981 (4) {\AA}, β = 96.65 (3)°, V = 3316 (3) {\AA}3, ρ = 1.36 g cm-3, Z = 4, Ru = 0.061, and Rw = 0.080. The ruthenium analogue 2a also crystallizes in the space group P21/c with a = 19.973 (2) {\AA}, b = 10.553 (2) {\AA}, c = 16.144 (1) {\AA}, β = 96.80 (7)°, V = 3378 (3) {\AA}3, ρ = 1.36 g cm-3, Z = 4, Ru = 0.070, and Rw = 0.068. Both complexes exhibit {"}zigzag{"} linear chains of closely spaced alternating cations and anions. Donor-acceptor interactions arise from close intermolecular contacts between the C6Me6 ligands of the dications and nitrogen atoms of the nonplanar dianion with dianions {"}bridging{"} the dications via three of its cyano groups. The complexes exhibit strong charge-transfer bands and are best described as donor-acceptor (DA) complexes with nominally doubly charged (D2-A2+) ground states and (D-A+) excited states. The difference between the charge-transfer absorption energies of 1 and 2 is equivalent to the difference in the solution reduction potentials of the isostructural (arene)2M2+ cations. The structure of the 19e (C6Me6)2Fe+ monocation, reported here for the first time, is essentially identical with that of the 18e dication, suggesting that the charge-transfer transitions of these DA complexes can occur without the formation of energetically unfavorable molecular conformations.",
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T2 - The zigzag linear chain complex [(C6Me6)2M2+][iso-C 4(CN)6 2-] (M = Fe, Ru)

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AU - Calabrese, J. C.

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N2 - Donor-acceptor solids [(C6Me6)2Me2+] [iso-C4(CN)6 2-]·MeNO2 (M = Fe, 1a; M = Ru, 2a) and [(C6Me3Hg)2M2+][iso-C 4(CN)6 2-] (M = Fe, 1b; M = Ru, 2b) prepared from (arene)2M2+ and iso-C4(CN)6 2- are described. Single-crystal X-ray studies show that Ia crystallizes in the space group P21/c with a = 19.875 (6) Å, b = 10.512 (2) Å, c = 15.981 (4) Å, β = 96.65 (3)°, V = 3316 (3) Å3, ρ = 1.36 g cm-3, Z = 4, Ru = 0.061, and Rw = 0.080. The ruthenium analogue 2a also crystallizes in the space group P21/c with a = 19.973 (2) Å, b = 10.553 (2) Å, c = 16.144 (1) Å, β = 96.80 (7)°, V = 3378 (3) Å3, ρ = 1.36 g cm-3, Z = 4, Ru = 0.070, and Rw = 0.068. Both complexes exhibit "zigzag" linear chains of closely spaced alternating cations and anions. Donor-acceptor interactions arise from close intermolecular contacts between the C6Me6 ligands of the dications and nitrogen atoms of the nonplanar dianion with dianions "bridging" the dications via three of its cyano groups. The complexes exhibit strong charge-transfer bands and are best described as donor-acceptor (DA) complexes with nominally doubly charged (D2-A2+) ground states and (D-A+) excited states. The difference between the charge-transfer absorption energies of 1 and 2 is equivalent to the difference in the solution reduction potentials of the isostructural (arene)2M2+ cations. The structure of the 19e (C6Me6)2Fe+ monocation, reported here for the first time, is essentially identical with that of the 18e dication, suggesting that the charge-transfer transitions of these DA complexes can occur without the formation of energetically unfavorable molecular conformations.

AB - Donor-acceptor solids [(C6Me6)2Me2+] [iso-C4(CN)6 2-]·MeNO2 (M = Fe, 1a; M = Ru, 2a) and [(C6Me3Hg)2M2+][iso-C 4(CN)6 2-] (M = Fe, 1b; M = Ru, 2b) prepared from (arene)2M2+ and iso-C4(CN)6 2- are described. Single-crystal X-ray studies show that Ia crystallizes in the space group P21/c with a = 19.875 (6) Å, b = 10.512 (2) Å, c = 15.981 (4) Å, β = 96.65 (3)°, V = 3316 (3) Å3, ρ = 1.36 g cm-3, Z = 4, Ru = 0.061, and Rw = 0.080. The ruthenium analogue 2a also crystallizes in the space group P21/c with a = 19.973 (2) Å, b = 10.553 (2) Å, c = 16.144 (1) Å, β = 96.80 (7)°, V = 3378 (3) Å3, ρ = 1.36 g cm-3, Z = 4, Ru = 0.070, and Rw = 0.068. Both complexes exhibit "zigzag" linear chains of closely spaced alternating cations and anions. Donor-acceptor interactions arise from close intermolecular contacts between the C6Me6 ligands of the dications and nitrogen atoms of the nonplanar dianion with dianions "bridging" the dications via three of its cyano groups. The complexes exhibit strong charge-transfer bands and are best described as donor-acceptor (DA) complexes with nominally doubly charged (D2-A2+) ground states and (D-A+) excited states. The difference between the charge-transfer absorption energies of 1 and 2 is equivalent to the difference in the solution reduction potentials of the isostructural (arene)2M2+ cations. The structure of the 19e (C6Me6)2Fe+ monocation, reported here for the first time, is essentially identical with that of the 18e dication, suggesting that the charge-transfer transitions of these DA complexes can occur without the formation of energetically unfavorable molecular conformations.

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